The invention provides a determination method of volatile organic acids in cigarette mainstream smoke. According to the determination method, the content of the volatile organic acids in total particulate matters of the cigarette mainstream smoke is determined by adopting vibration extraction and a gas chromatography-mass spectrometry technology. The determination method particularly comprises the following steps: (1) preparing a standard solution; (2) pretreating a sample; (3) qualitatively detecting the sample; (4) quantitatively detecting the sample; and (5) determining the content of the actual sample. According to the determination method of the volatile organic acids in the cigarette mainstream smoke, a standard sample addition method is used for qualifying and an internal sample standard curve method is used for quantifying; the recycling rate of the method is 97.5%-110.3%; the relative standard deviation (RSD%) of the method is 1.2%-8.5%; and the determination method has good sensitivity, accuracy and precision. Meanwhile, the method adopts the vibration extraction and a sample can be directly fed without deriving; and the determination method is simple and convenient to operate, and rapid in analyzing speed and is suitable for the determination of a large batch of the samples.